Shampoo



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and James Douglas N.J., assiguors to Colgate-Palm- New York, N.Y., acorporation of ABSTRACT OF THE DISCLOSURE A preferred conditioningshampoo is disclosed which contains (1) 12 to 30% of a detergent mixturewhich includes (a) a mixture of C -C alkyl di-lower-alkyl amine oxideshaving an average of 10 to 17 carbons in the alkyl group and a ratio ofC -C alkyl groups to C -C alkyl groups in the range of about 1:1 to 4:1,(b) a long chain amino of phosphoric carboxylic or sulfonic amphotericdetergent in acid or salt form and (c) a long chain quaternary ammoniumcationic detergent wherein the weight ratio of C -C alkyl di-lower-alkylamine oxide to cationic detergent is in the range of 0.6 to 24 and theweight ratio of C -C alkyl di-lower-alkyl amine oxide to amphotericdetergent is in the range of .5 to 12 and (11) water, the pH of theshampoo being in the range of 4.5 to 6.5. An aqueous acidic conditioningshampoo comprising a mixture of amine oxides and a quaternary ammoniumsalt is also set forth.

This invention relates to the production of conditioning shampoos.

The production of a good conditioning shampoo has been a goal ofchemists in the field of hair treatment for a long time. Shampoos whichthoroughly clean the hair usually leave it in a statically electrifiedstate, in which the individual hairs repel each other, or in a state inwhich simple combing produces this undesired electrification; in eithercase the hair is very diflicult to manage. To overcome this defect,creme rinses containing antistatic agents have been employed aftershampooing, but the use of these materials naturally requires additionaltime, effort and expense on the part of the user.

An effective conditioning shampoo must satisfy many requirements.Besides removing soil from the hair, it must yield a good foam, which islong-lasting and remains in place on the hair without running,comparable to the foam of current commercial shampoos. It must be easilyrinsed from the hair, with water, and the rinsing r must not only causethe foam to disappear but also eliminate the undesirable residual soapyfeel on the hair. It must leave the hair lustrous and with a pleasantfeel. It must reduce or eliminate the snarling of the hair whichordinarily results when the user runs her fingers repeatedly through thehair during shampooing which snarling makes it difficult for the user tocontinue working the hair with her fingers. It must promote easywet-combing of the washed and rinsed hair, allowing the strands of hairto slip easily on each other and to slip easily past the comb. It mustalso promote easy dry combing; thus, there should be little drag on thecomb during dry combing and the strands of hair should not tend to flyapart and become disaligned during or directly after the dry combingprocess. It must reduce static electrification of the hair; this can betested, for example, by dry combing a hair tress, containing severalhundred hairs, using a given number of strokes (e.g. 15 strokes) at agiven tempo with a comb made of hard rubber or other insulatingmaterial, then placing the back of the comb against the lower, free, endof the tress and moving the comb upward, with its back against the sideof the tress; the number of strands which follow the comb and becomedisaligned from the main body of the tress is an indication of thestatic electrification of the hair. The conditioning shampoo must alsobe substantially non-irritating and non-damaging to the eyes.

In accordance with one aspect of this invention, a conditioning shampoosatisfying the foregoing requirements comprises an acidic aqueousmixture containing a cationic detergent, an amphoteric detergent, and amixture of higher alkyl dialkyl amine oxides having an average of about10 to 17 carbon atoms in the higher alkyl group and in which the weightratio of higher alkyl groups containing 10 to 14 carbon atoms to thosecontaining 15 to 20 carbon atoms is about 1:1 to 4:1 (preferably about l/zzl to 3:1). Those higher alkyl dialkyl amine oxides in which thehigher alkyl is C to C are present in amount in the range of 0.6 to 24times (preferably more than 1 and still more preferably about 2 to 5times) the amount of the cationic agent, and in the range of /2 to 12times (preferably more than 1 and still more preferably about 2 to 5times) the amount of the amphoteric agent. The concentration of thecationic agent in the aqueous mixture, as used, is in the range of about0.5 to 5%, preferably about 2 to 4%, and the concentration of the othercomponents is such that the total amount of the detergents in themixture is in the range of about 12 to 30%, preferably about 15-25%. Itwill be appreciated, of course, that the composition may be supplied inmore highly concentrated form, for subsequent dilution with water.Preferably the total amount of the amine oxide is greater than thecombined amounts of the other detergents.

As indicated above, the shampoo is acidic, its pH being in the range ofabout 4 /2 to 6 /2. It is found that the performance (e.g. static, drycombing and foam properties) is significantly better when the shampoo isacidic than when it is neutral. A pH of about 5-6 is preferred. Anysuitable acid may be used for adjusting the pH, e.g. hydrochloric,citric acetic, sulfuric, alkylsulfuric (e.g. monoethyl sulfate),phosphoric, malic, etc.

The higher alkyl dialkyl amine oxide mixture preferably contains higheralkyl dimethylamine oxides, the higher alkyl groups being typicallydecyl, lauryl, myristyl, cetyl, stearyl, eicosyl or other higher alkylgroups of about 1020 carbon atoms, derived for example from tallow,hydrogenated tallow, coconut oil, etc. In place of one or both of themethyl groups there may be used ethyl, hy- (ll(1)Xy ethyl, hydroxypropylor similar lower alkyl radica s.

The amphoteric detergent is preferably a substituted aminocarboxylicacid having a substituent with a pendent long chain hydrophobic group,e.g. an alkyl of about 10-20 carbon atoms. Preferably the long chainsubstituent is connected to the amino nitrogen by a C-N bond and theamino and carboxyl groups are joined, through NC and CC bonds,respectively, by a divalent radical (e.g. an alkylene radical of 24carbon atoms, preferably 2 carbon atoms). Most preferably the aminogroup is monosubstituted by the long chain radical; however it is withinthe broader scope of the invention to use detergents in which the aminogroup is disubstituted, the second substituent being, for example,methyl or other lower alkyl or --RCOOH where R is a divalent radicalsuch as an alkylene radical of 2-4 carbon atoms. Betaines in which thereare three substituents on the amino nitrogen, may also be used. In themost preferred form of the invention, the long chain alkyl group isdirectly attached to the amino nitrogen; however, the attachment may bethrough intermediate structure such as through an imidazoline ring ofwhich the nitrogen of the amino acid is a part.

Examples of specific amphoteric detergents are N- higheralkyl-beta-aminopropionic acid; N-higher alkylbeta-iminodipropionicacid, and N-higher alkyl, N,N- dimethyl glycine (a betaine); the higheralkyl group may be, for example, that derived from coco fatty alcohol,lauryl alcohol, myristyl alcohol (or a lauryl myristyl mixture),hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols.

Other amphoteric detergents are the fatty imidazolines such as thosemade by reacting a long chain fatty acid (e.g. of to carbon atoms) withdiethylene triamine and a monohalocarboxylic acid having 2 to 6 carbonatoms, e.g. l-coco-S-hydroxyethyl-5-carboxymethylimidazoline; betainescontaining a sulfonic group instead of the carboxylic group; betaines inwhich the long chain substituent is joined to the carboxylic groupwithout an intervening nitrogen atom, e.g. inner salts of2-trimethylamino fatty acids such as Z-trimethylaminolauric acid, andcompounds of any of the previously mentioned types but in which thenitgrogen atom is replaced by phosphorus (e.g. carboxymethyl dimethyldodecyl phosphonium inner salt).

The amphoteric detergents are often supplied in the sodium or other saltforms, which may likewise be used in the practice of this invention. Itis preferred to use those amphoteric detergents which dissolve and foamreadily in acidified water.

The cationic detergents are quaternary ammonium salts having long chainhydrophobic radicals (e.g. alkyl radicals of 10-20 carbon atoms), suchas 1-methyl-1- higher alkylamidoethyl-2-higher alkylimidazolinium saltsin which the alkyl groups have, for example, 10-20 carbon atoms,ethoxylated long chain fatty quarternary ammonium compounds, higheralkyl benzyldimethylammonium salts, higher alkyl-pyridinium salts,higher alkyl isoquinolinium salts, di( higher alkyl) dimethylammoniumsalts, etc. The anion of the water-soluble quaternary ammonium compoundis most usually a chloride or methosulfate (OOS OCH ion, but other ionsmay be used as is well known in the art, e.g. bromide, phosphate,dialkyl phosphate or acetate ions.

The following examples illustrate this aspect of the invention further.

Example 1 A shampoo was prepared from the following constituents:

150 grams of a 30% solution in water of a higher alkyldimethylamineoxide mixture containing 60-65% lauryl dimethylamine oxide, -30%myristyl dimethylamine oxide and 10-15% cetyl dimethylamine oxide; 75grams of a 20% solution in water and isopropanol (in 1:1 ratio) of ahigher alkyl dimethylamine oxide containing 95% cetyl dimethylamineoxide, 3% lauryl dimethylamine oxide and 2% myristyl dimethylamineoxide; grams of a solution in water of a blend of N-higher alkylfl-aminopropionic acid and the corresponding N-higher alkylfl-iminodipropionate (the ratio of the former, monocarboxylic acid, tothe latter, dicarboxylic acid, being 10:1) in which the higher alkylradicals are lauryl and myristyl in ratio of 2.321 (known as Deriphat170-C); 20 grams of a mixture of 75% l-methyl l-long chainalkylamidoethyl-2-long chain alkylimidazolinium methosulfate (CulversoftS-75") in which the long chain alkyl radicals are 1.5% saturated C14,24% saturated C16, 4.5% ethylenically unsaturated C16, 25% saturated C18and 45% ethylenically unsaturated C18, 15% isopropanol, 3% glycerine and2% water; and 225 grams of deionized water.

The pH of the mixture was adjusted to 5.5 by addition of a small amountof 12 N hydrochloric acid.

Example 2 Example 1 was repeated except that in place of the 75 grams ofthe 20% solution of the blend of higher alkyl dimethylamine oxide (95%cetyl) there was used 300 grams of a 5% solution in water of that sameblend of amine oxides, and in place of the Culversoft S- there was used17 grams of Culversoft W5. (a product containing 86-88% of anethoxylated fatty quaternary ammonium chloride, 10-12% isopropanol, lessthan 1% free amine [calculated as trimethylamine, molecular weight 59],less than 2.5% amine hydrochloride [calculated as trimethylaminehydrochloride, molecular weight 95.5] The amount of separately addeddeionized water was reduced to 3 grams and the ingredients, beforeacidification, were heated together at 72 C. with moderate mixing in anopen vessel and then cooled to room temperature. 6 grams of water werethen added, to replace the 6 grams lost during the heating. The pH wasthen adjusted to 5 .5 by the addition of a small amount of 85%phosphoric acid (instead of the hydrochloric acid).

In a use test of the shampoo by a representative group of women, theshampoo was found to leave the hair soft, less dry, easy to comb, andfeeling as if it had been creme rinsed, and was reported by the women tobe significantly superior to current commercial shampoos.

The shampoos of this invention, while safe to the eyes, have thedesirable property of causing slight stinging when present in high,concentration in the eyes; this warns the user to rinse out the shampoofrom her eyes promptly so that there is little or no undesired removalof natural fats and oils from the tissue.

Another aspect of this invention relates to conditioning shampoocompositions in which the amphoteric detergent may be omitted entirelyor used in reduced amount. In this case there is included in the shampoocompositions a significant amount of higher alkyl dialkylamine oxidehaving at least 18 carbon atoms in the higher alkyl group, i.e. at least5%, and preferably at least about 10%, of the total amount of the higheralkyl dialkyl amine oxides should be such a C (01' higher) higher alkylamine oxide. In such compositions the ratio of the total amount of amineoxides to the amount of the cationic agent should be at least 08:1 andless than 30:1 (preferably more than 1:1 and still more preferably about2:1 to 5:1); the average molecular weight of the amine oxides is atleast about 230 (preferably above 240), the average molecular weight ofthe higher alkyl groups is preferably at least and more preferably atleast and the weight ratio, in the amine oxides, of higher alkyl groupscontaining 10 to 12 carbon atoms to those containing 13 to 20 carbonatoms is in the range of about 3:12 to 13:2 (preferably about 2:1 to1:2). The compositions made without the amphoteric detergent do not,however, have all the excellent qualities of the previously describedcompositions. They are not quite as good with respect to foam volume,foam texture, foam density, feel and slip.

The following example illustrates this aspect of the invention further.

Example 3 A shampoo was produced by mixing the following constituents:

15 parts of the 30% aqueous solution of the alkyldimethylamine oxide(60-65% lauryl, 25-30% myristyl, 10% cetyl) of Example 1;

5 parts of the 20% solution of higher alkyl dimethylamine oxide (95%cetyl, 3% myristyl, 2% lauryl) described in Example 1;

3.4 parts of a 30% solution in water of mixed higher alkyldimethylamineoxides containing 10-15% of lauryl dimethylamine oxide, 55-60% ofmyristyl dimethylamine oxide and 25-30% of cetyl dimethylamine oxide;

5.3 parts of a 19% suspension in water of mixed higher alkyldimethylamine oxides containing 91% stearyl dimethylamine oxide, 8%cetyl dimethylamine oxide and 1% myristyl dimethylamine oxide;

2 parts of the suspension of quaternary compound of Example 1;

19.4 parts of water.

The pH of the mixture was adjusted to 5.5 by the addition of a smallamount of 12 N HCl.

Example 4 A shampoo was produced by mixing the following constituents:

15 parts of the 30% aqueous solution of the alkyldimethylamine oxide (6065% lauryl, 25-30*% myristyl, cetyl) of Example 1;

20 parts of the 5% solution in water of higher alkyl dimethylamine oxide(95% cetyl, 3% myristyl, 2% lauryl) described in Example 2;

3.4 parts of a 30% solution in water of mixed higher alkyldimethylamineoxides containing 10-15% of lauryl dimethylamine oxide, 55-60% ofmyristyl dimethylamine oxide and 25-30% of cetyl dimethylamine oxide;

4 parts of a 25% suspension in water of mixed higher alkyl dimethylamineoxides containing 95% stearyl dimethylamine oxide and 5% cetyldimethylamine oxide; 1.7 parts of the Culversoft W.S. 90; 6 parts ofwater, and a small quantity of citric acid sufficient to lower the pH to5.5. Small amounts of coloring agent (FD. & C, Blue #1) and perfume werealso included.

Unless otherwise indicated, all proportions set forth herein are byweight.

Although the present invention has been described with reference toparticular embodiments and examples, it will be apparent to thoseskilled in the art that variations and modifications can be substitutedtherefor without departing from the principles and true spirit of theinvention.

Having thus described the invention, what is claimed is:

1. An aqueous hair conditioning shampoo which consists essentially of anacidic aqueous mixture of (a) a mixture of higher alkyl, di(C C alkyl)amine oxide detergents having an average of about 10 to 17 carbon atomsin said higher alkyl group and in which the Weight ratio of higher alkylgroups having 10 to 14 carbon atoms to those having 15 to carbon atomsis about 1:1 to 4:1; (b) an amphoteric detergent selected from the groupconsisting of N-higher alkyl aminopropionic acid, N-higher alkyliminodipropionic acid, and mixtures thereof, said higher alkyl groupcontaining 10' to 20 carbon atoms; and (c) about 0 .5 to 5% by weight ofa cationic, quaternary ammonium detergent having a long chainhydrophobic radical of 10 to 20 carbon atoms in its molecular structure,the weight of C to C alkyl di(C C alkyl) amine oxide being present inthe range of 0.6 to 24 times the weight of cationic detergent and in therange of /2 to 12 times the weight of the amphoteric detergent, thetotal concentration of the detergents being 12% to 30 by Weight of theshampoo, said shampoo having a pH of 4.5 to 6.5 and yielding a good foamwith good cleansing power and leaving the hair in an easily combablecondition on rinsing with water without the need for a subsequentantistatic creme rinse.

2. A composition as set forth in claim 1 in which the lower alkyls ofsaid amine oxide are methyl, the weight ratio of higher alkyl groupshaving 10 to 14 carbon atoms to those having 15 to 20 carbon atoms isabout l /2:1 to 3:1, and the weight of C -C alkyl dimethyl amine oxideis about 2 to 5 times the weight of the cationic detergent and about 2to 5 times the weight of the amphoteric detergent.

3. A composition as set forth in claim 2 in which said amine oxides arepresent in an amount greater than the total weight of said otherdetergents.

References Cited UNITED STATES PATENTS 3,296,145 l/1967 Findlan et a1.252106 LEON D. ROSDOL, Primary Examiner W. SCHULZ, Assistant ExaminerUS. Cl. X.R.

